JP2001011732A - Copolymer elastic fiber having good coverability at low temperature - Google Patents
Copolymer elastic fiber having good coverability at low temperatureInfo
- Publication number
- JP2001011732A JP2001011732A JP11181930A JP18193099A JP2001011732A JP 2001011732 A JP2001011732 A JP 2001011732A JP 11181930 A JP11181930 A JP 11181930A JP 18193099 A JP18193099 A JP 18193099A JP 2001011732 A JP2001011732 A JP 2001011732A
- Authority
- JP
- Japan
- Prior art keywords
- elastic fiber
- cheese
- diol
- yarn
- covering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、伸長回復性の優れ
て改良されたポリウレタンウレア弾性繊維に係り、詳し
くは弾性繊維が低温下で加工されるにおいても、逆巻き
による糸切断が低減した弾性繊維チーズ巻体の解除、弛
み糸切れの低減した被覆加工弾性糸のチーズ巻きなどが
できるポリウレタンウレア弾性繊維に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane urea elastic fiber having improved elongation and recovery properties, and more particularly to an elastic fiber having reduced thread breakage due to reverse winding even when the elastic fiber is processed at a low temperature. The present invention relates to a polyurethane urea elastic fiber capable of releasing a cheese roll, winding a coated elastic yarn with reduced slack yarn breakage, and the like.
【０００２】[0002]
【従来の技術】弾性繊維は伸長回復性を要求されるレッ
グ、パンテイーストッキング、おむつカバー等に使用さ
れる。これらの製品では、弾性繊維は通常他の繊維との
複合された糸が用いられている。弾性繊維と他の繊維と
の複合は、弾性繊維の周りに他の糸を単層に被覆するシ
ングルカバードヤーン（以下ＳＣＹと略す）、２層の糸
を被覆するダブルカバードヤーン、短繊維糸で被覆した
コアスパンヤーンなどがある。そして、弾性繊維のカバ
リング乃至被覆加工（以下カバリング加工という）は、
弾性繊維を延伸した状態で被覆し、ついで加工糸たるカ
バリング糸もしくは被覆糸は一定比率収縮させられた後
にチーズに巻き取っている。これらのカバリング加工は
連続して行われており、特に、短時間での伸長回復性に
優れた弾性繊維が恒常的に求められている。2. Description of the Related Art Elastic fibers are used for legs, pante yeast hooks, diaper covers, etc., which require elongation recovery. In these products, as the elastic fiber, a yarn composited with another fiber is usually used. The composite of the elastic fiber and the other fiber is a single covered yarn (hereinafter abbreviated as SCY) covering the other layer in a single layer around the elastic fiber, a double covered yarn covering the two layers of the yarn, and a short fiber yarn. Coated core spun yarns and the like. The covering or covering process (hereinafter referred to as covering process) of the elastic fiber is
The elastic fiber is coated in a stretched state, and then the covering yarn or the coated yarn, which is a processing yarn, is shrunk to a certain ratio and then wound around a cheese. These covering processes are performed continuously, and in particular, elastic fibers excellent in elongation and recovery in a short time are constantly required.
【０００３】特開平７−２７８９８３号公報には、伸長
回復性に優れた弾性繊維を得る目的で、低分子量のポリ
テトラメチレンエーテルグリコール（以降ＰＴＭＧと略
す）を用いたり、高分子量部分を除去したＰＴＭＧを用
いる弾性繊維の製造方法が記載されている。特開平１ー
２８４５１８号公報は、テトラヒドロフラン（以降ＴＨ
Ｆと略す）の開環重合に際し、ネオペンチルグリコール
を共重合し、側鎖にメチル基を持たせる事で弾性繊維に
伸長回復性を付与する技術について開示している。[0003] Japanese Patent Application Laid-Open No. 7-278983 discloses the use of low-molecular-weight polytetramethylene ether glycol (hereinafter abbreviated as PTMG) or removal of a high-molecular-weight portion in order to obtain an elastic fiber excellent in elongation recovery. A method for producing elastic fibers using PTMG is described. JP-A-1-284518 discloses tetrahydrofuran (hereinafter referred to as TH).
A technique for imparting elongation recovery to elastic fibers by copolymerizing neopentyl glycol in the ring-opening polymerization of (abbreviated as F) and imparting a methyl group to the side chain is disclosed.
【０００４】弾性繊維の利用が増加するのにともなっ
て、弾性繊維のカバリング加工における糸切れの問題が
クローズアップされている。特に寒冷期の朝にカバリン
グ加工が行われる場合の加工の始動期に発生する弾性繊
維チーズの逆巻きによる弾性繊維の糸切れの多発とカバ
リング糸のチーズ巻き取り工程でのカバリング糸のたる
みによるカバリング糸切れの多発の問題が深刻である。[0004] As the use of elastic fibers increases, the problem of thread breakage in the covering process of elastic fibers has been highlighted. Especially when the covering process is performed in the morning of the cold season, the elastic fiber cheese is frequently wound in the reverse winding of the elastic fiber cheese which occurs at the start of processing, and the covering yarn due to the slack of the covering yarn in the cheese winding process of the covering yarn. The problem of frequent cuts is serious.
【０００５】ここで「逆巻き」とは、よく知られている
ように、弾性繊維がチーズから解除されるとき、チーズ
の表面からの糸離れが悪くなり糸が逆方向に巻き取れれ
る現象である。一方、弛みによる糸切れは、寒冷期下の
加工のスタートアップ期での弾性繊維の短時間内におけ
る伸長回復性の低下に起因する。汎用のポリウレタン弾
性糸の伸長回復速度の温度依存性を観測すると、以下に
例示するように、０〜２０℃の室温下でも、伸長後１０
秒以内の期間中に観測される弾性回復速度が弾性繊維の
温度が低温側にシフトするにしたがって劇的に低下する
ことが判明した。[0005] Here, "reverse winding" is a well-known phenomenon that when the elastic fiber is released from the cheese, the yarn separation from the cheese surface becomes worse and the yarn is wound in the reverse direction. . On the other hand, the yarn breakage due to slackness is caused by a decrease in the elongation and recovery of the elastic fiber in a short period of time during the start-up period of the processing in the cold period. When observing the temperature dependence of the elongation recovery rate of a general-purpose polyurethane elastic yarn, as illustrated below, even at room temperature of 0 to 20 ° C., the elongation recovery speed is 10%.
It was found that the elastic recovery rate observed during the sub-second period decreased dramatically as the temperature of the elastic fiber shifted to lower temperatures.
【０００６】例えば、２０ｄの弾性繊維を初期長１００
mm採取し、これを２００mmに伸ばした状態で所定温度下
で１６時間放置した後に張力を解き、１０秒後の長さ
（Ｌ）を測定し（Ｌ−１００）（ｍｍ）の値（以下、伸
長回復性という：数値が小さい程回復速度特性が大き
い）を比較すると、２０℃で低温伸長回復率が１０mmで
ある数平均分子量１９００であるＰＴＭＧを、ジオール
成分とし４−、４’ジフェニルメタンジイソシアネート
をソフトセグメントとし、鎖延長剤としてエチレンジア
ミンを用い、乾式紡糸したポリウレタンウレア弾性繊維
は、高分子量ＰＴＭＧ含量が多く、１０℃で５３．４m
m、０℃では８１mmと急激に大きくなり、温度の低下と
ともに伸長弾性回復性が急激に低下する。For example, an elastic fiber of 20 d has an initial length of 100
The sample was taken out at a predetermined temperature in a state where the sample was stretched to 200 mm and left at a predetermined temperature for 16 hours. The tension was released, and the length (L) after 10 seconds was measured. When the value is smaller, the PTMG having a number average molecular weight of 1900 and a low temperature elongation recovery rate of 10 mm at 20 ° C. is used as a diol component, and 4-, 4′-diphenylmethane diisocyanate is used. The polyurethane urea elastic fiber spun as a soft segment and using ethylenediamine as a chain extender has a high molecular weight PTMG content and a high content of 53.4 m at 10 ° C.
When the temperature is 0 ° C. and m, it rapidly increases to 81 mm, and the elongation elastic recovery rapidly lowers as the temperature decreases.
【０００７】このように、弾性繊維の伸長回復性は温度
の低下によって急激に低下するとの知見から、問題点は
以下のように推察される。寒冷時の夜間気温によって弾
性繊維チーズは温度の低下をきたし、弾性繊維の伸長回
復性は大幅に低下している。また弾性繊維チーズは、カ
バリング開始時の暖房でチーズ表面の弾性糸は暖まるも
のの、内部は依然として冷えており、かかる部分がカバ
リング糸のチーズ巻き取り工程で低収縮となり、瞬く間
にたるみを生じ、隣接する突起物に引っかかったり、た
るみ部が絡まってガイドに引っかかったり、弛み部が一
度にローラに取り込まれカバリング糸を切断してしま
う。[0007] As described above, from the knowledge that the elongation recoverability of the elastic fiber sharply decreases with a decrease in temperature, the problem is presumed as follows. The temperature of the elastic fiber cheese decreases due to the cold nighttime temperature, and the elastic recovery of the elastic fiber is greatly reduced. In addition, the elastic fiber cheese, although the elastic yarn on the cheese surface is warmed by heating at the start of covering, the inside is still cool, and such a portion becomes low shrinkage in the cheese winding process of the covering yarn, causing slack in an instant, An adjacent protrusion may be caught, a slack portion may be entangled with a guide, or a slack portion may be taken into the roller at one time to cut the covering yarn.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、弾性繊維の
カバリング加工が寒冷期に遭遇する低温の下で行われて
も、チーズ巻体が解除に逆巻きを起こさず、かつ被覆後
に弛み糸切れを起こさないで巻き上げチーズ上に安定し
て引き取ることができるポリウレタンウレア弾性繊維の
提供を課題とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a roll of cheese, which does not cause reverse winding of the cheese roll even if the covering process of the elastic fiber is performed at a low temperature which is encountered in a cold season, and that the loosened yarn breaks after coating. It is an object of the present invention to provide a polyurethane urea elastic fiber that can be stably taken up on a rolled cheese without causing wrinkles.
【０００９】本発明の具体的な課題は、弾性繊維の温度
低下に伴う、急激な伸長回復性、特に伸長回復速度の低
下を改善し、粘着にともなうチーズでの逆巻きが少ない
ポリウレタンウレア系弾性繊維を提供することにある。[0009] A specific object of the present invention is to improve polyurethane urea-based elastic fiber, which is capable of improving a rapid elongation-recovery property, particularly a reduction in elongation-recovery rate, associated with a decrease in temperature of the elastic fiber, and having less reverse winding of cheese due to sticking. Is to provide.
【００１０】[0010]
【課題を解決するための手段】本発明は、特にメチル基
側鎖を有するアルキレンジオールをソフトセグメント形
成成分として用い、繊維を形成するポリウレタンウレア
中に存在する環状オリゴマーの上限許容量を極めて精緻
に制御することによって達成することができる。According to the present invention, an alkylene diol having a methyl group side chain is used as a soft segment-forming component, and the upper limit of the amount of cyclic oligomers present in polyurethane urea forming a fiber is extremely finely adjusted. This can be achieved by controlling.
【００１１】すなわち本発明は、繰り返し単位が９以下
である環状オリゴマーの含有量が１．５重量％以下であ
りメチル基側鎖を有する共重合ポリアルキレンエーテル
ジオールをジオール成分として構成されたポリウレタン
ウレアからなる低温カバリング性に優れたポリウレタン
ウレア弾性繊維である。本発明の弾性繊維を構成するポ
リウレタンウレアは、メチル基側鎖を有するポリアルキ
レンエーテルジオールと有機ジイソシアネートとのウレ
タン結合を有するソフトセグメントと、ソフトセグメン
ト両末端のイソシアネートと２官能有機ジアミンとのウ
レア結合よりなるハードセグメントからなる。That is, the present invention provides a polyurethane urea comprising a copolymerized polyalkylene ether diol having a content of a cyclic oligomer having 9 or less repeating units of 1.5% by weight or less and having a methyl group side chain as a diol component. It is a polyurethane urea elastic fiber having excellent low-temperature covering properties. The polyurethane urea constituting the elastic fiber of the present invention includes a soft segment having a urethane bond between a polyalkylene ether diol having a methyl group side chain and an organic diisocyanate, and a urea bond between an isocyanate at both ends of the soft segment and a bifunctional organic diamine. It consists of hard segments.
【００１２】このハードセグメントは、相互に水素結合
を形成し、分子相互結合点、ゴムで言う架橋点を形成
し、弾性性能を繊維に発現せしめている。本発明では、
重合体のソフトセグメント形成成分としてメチル基側鎖
を有するアルキレンジオールを用いる。メチル基側鎖を
有するアルキレンジオールを採用することで、重合体に
結晶の成長を阻害して、得られる弾性繊維の伸度を大き
くすると共に、低温時の伸長回復性が顕著に維持するこ
とができる。一方メチル基側鎖を有するポリアルキレン
エーテルジオールの共重合では、環状オリゴマーの生成
が増加する傾向にあり、環状オリゴマーの弾性繊維表面
へのブリードによって弾性繊維表面の粘着性が上昇し、
特に表面へのブリード量が一定以上になると、急激に弾
性繊維同士の粘着性が強くなり、粘着によるチーズでの
逆巻きによる糸切れが起こりやすくなる。The hard segments form hydrogen bonds with each other, form molecular mutual bonding points, and cross-linking points referred to as rubber, so that the fibers exhibit elasticity. In the present invention,
An alkylene diol having a methyl group side chain is used as a soft segment forming component of the polymer. By employing an alkylene diol having a methyl group side chain, the growth of crystals in the polymer is inhibited, the elongation of the obtained elastic fiber is increased, and the elongation recovery at low temperatures is significantly maintained. it can. On the other hand, in the copolymerization of a polyalkylene ether diol having a methyl group side chain, the generation of cyclic oligomers tends to increase, and the bleeding of the cyclic oligomer onto the elastic fiber surface increases the adhesiveness of the elastic fiber surface,
In particular, when the amount of bleeding to the surface exceeds a certain level, the adhesiveness of the elastic fibers becomes sharply sharp, and yarn breakage due to reverse winding of the cheese due to the adhesiveness easily occurs.
【００１３】寒冷時の低温度下において、カバリング性
の良好な弾性繊維を得るためには、用いられるジオール
のメチル基側鎖が、低温伸長時に結晶形成をする共重合
量以上であり、また弾性繊維の粘着性を大きくする環状
オリゴマー含有量を少なくすることが重要であるが、
１．５重量％以下にすることが特に重要である。共重合
に使用するアルキレン基としては、得られるポリウレタ
ン弾性繊維の耐水性、耐光性、耐摩耗性、および弾性機
能の観点から、アルキレン基の１つがテトラメチレン基
であり、他のアルキレン基と共重合していることが好ま
しい。共重合するアルキレン基として、２，２−ジメチ
ルプロピレン基、３−メチルペンタメチレン基および３
−メチルテトラメチレン基が好ましい。特に好ましく
は、２，２−ジメチルプロピレン基である。[0013] In order to obtain an elastic fiber having good covering properties at a low temperature in a cold state, the diol used has a methyl group side chain which is equal to or more than a copolymerization amount which forms crystals at low temperature elongation. It is important to reduce the cyclic oligomer content that increases the fiber's tackiness,
It is particularly important that the content be 1.5% by weight or less. As the alkylene group used for the copolymerization, one of the alkylene groups is a tetramethylene group and the other alkylene group is copolymerized from the viewpoints of water resistance, light resistance, abrasion resistance, and elasticity of the obtained polyurethane elastic fiber. Preferably, it is polymerized. As the alkylene group to be copolymerized, 2,2-dimethylpropylene group, 3-methylpentamethylene group and 3
-A methyltetramethylene group is preferred. Particularly preferred is a 2,2-dimethylpropylene group.
【００１４】また、テトラメチレン基以外のアルキレン
エーテルユニットは、４モル％以上、かつ４０モル％以
下含むことが好ましい。好ましくは８モル％以上、かつ
３０モル％以下である。４モル％未満では、低温伸長時
テトラメチレン基が結晶を形成しやすく、伸長回復性が
低下しカバリング糸のたるみを生じ、４０モル％を超え
ると弾性繊維の強度または伸度が低下する傾向がある。The alkylene ether unit other than the tetramethylene group preferably contains at least 4 mol% and at most 40 mol%. Preferably it is 8 mol% or more and 30 mol% or less. If the amount is less than 4 mol%, the tetramethylene group tends to form a crystal at the time of low-temperature elongation, the elongation-recovery property decreases, and the covering yarn becomes slack. If the amount exceeds 40 mol%, the strength or elongation of the elastic fiber tends to decrease. is there.
【００１５】共重合ポリアルキレンエーテルジオール
は、繰り返し単位９以下のオリゴマー含有量が１．５重
量％以下であり、特に好ましくは１．０重量％以下であ
る。オリゴマー含有量が１．５重量％以下では弾性繊維
表面の粘着性が急激に低下し、逆巻きの改善が著しい。
またテトラメチレン基以外のアルキレンエーテルユニッ
トが、上記のモル％の範囲内で存在する混合ポリアルキ
レンエーテルジオールであっても、環状オリゴマーの含
有量が１．５重量％以下であればこれを使用してもよ
い。[0015] The copolymerized polyalkylene ether diol has an oligomer content of not more than 9 repeating units of 1.5% by weight or less, particularly preferably 1.0% by weight or less. When the oligomer content is 1.5% by weight or less, the tackiness of the surface of the elastic fiber is rapidly reduced, and the reverse winding is remarkably improved.
Further, even if the alkylene ether unit other than the tetramethylene group is a mixed polyalkylene ether diol present in the above-mentioned mol% range, it is used if the content of the cyclic oligomer is 1.5% by weight or less. You may.
【００１６】本発明で使用される共重合ポリアルキレン
エーテルジオールの数平均分子量（Ｍｎ）は、１０００
〜４００００が好ましい。Ｍｎが１０００より小さい場
合繰り返し単位９以下の環状オリゴマー量が多くなり、
４０００より大きいとヒステリシスロスや低温下の伸長
回復性が悪くなり好ましくない。本発明の弾性繊維は、
数平均分子量が１０００〜４００００、繰り返し単位が
９以下である環状オリゴマーの含有量が１．５重量％を
超えないメチル基側鎖を含む共重合ポリアルキレンエー
テルジオールをジオール成分とし、これに過剰の有機ジ
イソシアネート 、例えば４、４’−ジフェニルメタン
ジイソシアネートを反応させ両末端イソシアネートプレ
ポリマーを常法によって合成する。ジオールとジイソシ
アネートのモル比は１．２〜１．８であり、ソフトセグ
メントの分子量は４０００〜８０００の範囲に調整でき
る。環状オリゴマーはジイソシアネートと反応せず、そ
のままプレポリマーの中に取り込まれる。次いで、両末
端イソシアネートプレポリマーと２官能有機ジアミンを
適当量の１官能有機アミンの存在下に反応せしめること
によってポリウレタンウレアを得る。プレポリマー、ジ
アミンは溶剤に溶かし、混合する事でポリウレタンウレ
ア紡糸原液とすることができ、汎用の乾式もしくは湿式
紡糸を適用することでポリウレタンウレア弾性繊維を得
ることができる。The number average molecular weight (Mn) of the copolymerized polyalkylene ether diol used in the present invention is 1000
~ 40,000 is preferred. When Mn is smaller than 1000, the amount of cyclic oligomers having a repeating unit of 9 or less increases,
If it is larger than 4000, hysteresis loss and elongation recoverability under low temperature become poor, which is not preferable. The elastic fiber of the present invention,
A copolymerized polyalkylene ether diol containing a methyl group side chain having a number average molecular weight of 1,000 to 40,000 and a cyclic oligomer having a repeating unit of 9 or less and not exceeding 1.5% by weight is used as a diol component, and an excess of An organic diisocyanate, for example, 4,4'-diphenylmethane diisocyanate is reacted to synthesize an isocyanate prepolymer at both ends by a conventional method. The molar ratio between the diol and the diisocyanate is 1.2 to 1.8, and the molecular weight of the soft segment can be adjusted in the range of 4000 to 8000. The cyclic oligomer does not react with the diisocyanate and is taken into the prepolymer as it is. Next, a polyurethane urea is obtained by reacting the isocyanate prepolymer at both ends with a bifunctional organic diamine in the presence of an appropriate amount of a monofunctional organic amine. The prepolymer and diamine can be dissolved in a solvent and mixed to form a polyurethaneurea spinning stock solution, and a polyurethaneurea elastic fiber can be obtained by applying general-purpose dry or wet spinning.
【００１７】上述のポリウレタンウレア重合体の調整に
おいて、用いられるメチル基側鎖を有する共重合ポリア
ルキレンエーテルジオールは、いかなる方法で製造され
たものであってもよい。特開昭５８−９５０３６号公報
に開示されているヘテロポリ酸を触媒とし、ＴＨＦとネ
オペンチルグリコール、３−メチル−１、５−ペンタン
ジオール、またはそれらの脱水環状化合物、例えば３、
３−ジメチルオキセタンを反応させることによって製造
される。その共重合ジオールは、所定の分子量、共重合
比となるように、反応の方法および条件を種々変化させ
ることによって、繰り返し単位９以下の環状オリゴマー
含有量が１．５重量％以下のジオールを得ることができ
る。In the preparation of the polyurethaneurea polymer described above, the copolymerized polyalkylene ether diol having a methyl group side chain used may be produced by any method. Using a heteropoly acid disclosed in JP-A-58-95036 as a catalyst, THF and neopentyl glycol, 3-methyl-1,5-pentanediol, or a dehydrated cyclic compound thereof, for example, 3,
It is produced by reacting 3-dimethyloxetane. The copolymerized diol is obtained by variously changing the reaction method and conditions so that a predetermined molecular weight and a copolymerization ratio are obtained, thereby obtaining a diol having a cyclic oligomer content of not more than 9 repeating units and not more than 1.5% by weight. be able to.
【００１８】繰り返し単位９以下の環状オリゴマー含有
量の低減は、薄膜減圧処理における圧力と温度、時間に
よって調整できる。またオクタン洗浄によっても環状オ
リゴマー含有量を減少せしめることができる。本発明の
ポリウレタンウレア重合体の合成に使用される有機ジイ
ソシアネート化合物は、４、４’−ジフェニルメタンジ
イソシアネート、２、４−トルエンジイソシアネート、
１、４−フェニレンジイソシアネート、４，４’−シク
ロヘキシルメタンジイソシアネ−ト等があげられる。The cyclic oligomer content of the repeating unit 9 or less can be reduced by adjusting the pressure, temperature, and time in the thin-film decompression treatment. The cyclic oligomer content can also be reduced by octane washing. The organic diisocyanate compound used for synthesizing the polyurethaneurea polymer of the present invention includes 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate,
1,4-phenylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate and the like can be mentioned.
【００１９】２官能有機ジアミンとしては、ヒドラジ
ン、エチレンジアミン、１、２−プロピレンジアミン、
１、４−ブチルジアミン、１、６−ヘキサメチレンジア
ミン、１、３−シクロヘキシルジアミン、４、４’ジア
ミノジフェニルメタン、４、４’−ジアミノジシクロヘ
キシルメタンがあげられる。これらジアミンのうち、良
好な物性を与えるものとして、エチレンジアミン、１，
２−プロピレンジアミン、１、６−ヘキサメチレンジア
ミン、またはこれらの混合物が好ましい。Examples of the bifunctional organic diamine include hydrazine, ethylenediamine, 1,2-propylenediamine,
1,4-butyldiamine, 1,6-hexamethylenediamine, 1,3-cyclohexyldiamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodicyclohexylmethane. Among these diamines, ethylenediamine, 1,
2-propylenediamine, 1,6-hexamethylenediamine, or mixtures thereof are preferred.
【００２０】本発明で用いられる１官能有機アミンとし
ては、ジエチルアミン、ジメチルアミン、ジブチルアミ
ン、ジエタノールアミン等を用いることができる。ポリ
ウレタンウレア重合体の合成に用いられる不活性極性溶
媒としては、ジメチルホルムアミド、ジメチルアセトア
ミド、ジメチルスルホキシド等があげられる。As the monofunctional organic amine used in the present invention, diethylamine, dimethylamine, dibutylamine, diethanolamine and the like can be used. Examples of the inert polar solvent used for the synthesis of the polyurethane urea polymer include dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like.
【００２１】以上のようにして調整された紡糸原液に
は、酸化防止剤、紫外線吸収剤、黄変防止剤などが添加
される。各種添加剤を混合した紡糸原液はフィルターで
異物を除去した後、一定量を送液し、加熱した空気、或
いは不活性ガスなどの気流中に、ノズルを通し押し出
す。紡糸原液が押し出され形成されフィラメント（繊
維）は、紡口下熱気流で極性溶媒が蒸散して、糸状とな
った後、仮撚の適用をうけて収束させられた後、油剤を
付与され所定の特性を有する弾性繊維が得れる。An antioxidant, an ultraviolet absorber, an anti-yellowing agent, and the like are added to the spinning dope prepared as described above. After removing foreign matter with a filter, a certain amount of the spinning dope mixed with various additives is fed, and then extruded through a nozzle into a stream of heated air or an inert gas. The spinning solution is extruded to form a filament (fiber). After the polar solvent evaporates in a hot air stream under the spinneret, the filament is formed into a thread-like form, which is then subjected to false twist and then converged. An elastic fiber having the following characteristics is obtained.
【００２２】[0022]
【実施例】以下に実施例等に基づいて本発明をより具体
的に説明するが、本発明はこれら実施例等により何ら制
限を受けるものではない。なお、以下の実施例における
測定値は、以下に説明する測定方法によりもとめられた
ものである。 （１）重量平均分子量、数平均分子量、及びその比であ
る多分散度ｄの測定：ゲルパーミッションクロマトグラ
フィー（ＧＰＣ）により以下の条件で測定した。ＰＴＭ
Ｇ固体を３ｍＬのＴＨＦに溶解し、その溶液１ｍＬをＧ
ＰＣに注入し、測定した。ＧＰＣ測定条件及び装置概要
は以下の通りである。溶媒はＴＨＦ、溶媒流速１ｍＬ/m
in、カラム温度４０℃でおこなった。装置はシステムコ
ントローラーとしてＳＣＬ−６Ｂ（島津製）カラムオー
ブンとしてＣＴＯ−６Ａ（島津製）、検出器は示差屈折
計ＲＩＤ−６Ａ（島津製）、カラムはＴＳＫ−ｇｅｌＧ
３０００ＨXL×２本（東ソー製）を用い計測し、データ
ー処理を行って平均分子量、多分散度を算出した。 （２）弾性繊維のカバリング時の糸切性評価：弾性繊維
チーズはポリエチレンの袋の中で２５℃・１ヶ月間貯蔵
し、しかる後カバリングを行う。カバリング加工はオゼ
キテクノ（株）製カバリングマシンＯＮ−７４１Ｓに、
２０デニールの２フィラメントの弾性繊維を８５ｍｍ
φ、幅５０ｍｍの紙管に巻き取とった弾性繊維チーズ、
ポリアミド繊維（旭化成工業（株）製、レオナ１０ｄ／
５ｆ）のチーズを取り付け、１６時間１０℃に保つ。し
かる後１５℃に外気温を上げ、５分後に弾性繊維のカバ
リングを開始する。カバリング条件はドラフト率２．
７、撚り数１６００Ｔ／ｍ、シングルカバーＳ撚り、Ｚ
撚りとする。カバリングされたＳＣＹの巻き取り比率
は、カバリング出ロール速度に対し、０．９５倍とし
た。合計１０錘のカバリング機にチーズを仕掛け、カバ
リング開始後１０分運転させ、逆巻きや弛みなどで糸が
切れて、加工機が停止する錘数を数え停止錘数が１０％
を超える弾性繊維は不適当であると判定する。 （３）環状オリゴマーの測定：共重合ＰＴＭＧを２倍量
のクロロホルムで希釈し、ガスクロ｛カラム：シリコン
ＳＥ−３０ １０ｗｔ％／クロモソルブＷＨＰ×１ｍ
（ガラス）カラム温度２９５℃｝で行った。 （４）組成比率の測定 1 Ｈ．13Ｃ−ＮＭＲ（日本電子（株）製 ＪＥＯＬ−Ｇ
Ｘ ４００）によって求めた。 [ 実施例１] （ポリウレタンウレア弾性繊維の製造）攪拌装置と環流
冷却器とを付けた容器に、ＴＨＦ５００ｇとネオペンチ
ルグリコール５６ｇを仕込む。３４０℃で３時間加熱し
て無水状態にした隣タングステン酸を５００ｇ加え、乾
燥窒素ガス雰囲気下、６０℃に保持して１０時間攪拌し
反応させた後、室温で静置すると二相に分離する。上層
を分離し、未反応のＴＨＦ、ネオペンチルグリコールを
蒸留により除き、透明で粘性のあるポリアルキレンエー
テルジオール１４０ｇを得た。分析の結果数平均分子量
は２０００、側鎖含有単位の比率１５％、繰り返し単位
９以下の環状オリゴマーの含有量は４％であった。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by these examples. In addition, the measured values in the following examples are obtained by the measuring method described below. (1) Measurement of weight average molecular weight, number average molecular weight, and polydispersity d as a ratio thereof: Measured by gel permission chromatography (GPC) under the following conditions. PTM
G solid was dissolved in 3 mL of THF, and 1 mL of the solution was dissolved in G
It was injected into a PC and measured. The GPC measurement conditions and the outline of the apparatus are as follows. Solvent is THF, solvent flow rate 1mL / m
in, at a column temperature of 40 ° C. The instrument is SCL-6B (manufactured by Shimadzu) as a system controller, CTO-6A (manufactured by Shimadzu) as a column oven, the detector is a differential refractometer RID-6A (manufactured by Shimadzu), and the column is TSK-gelG.
The measurement was performed using two 3000 HXL (manufactured by Tosoh), and data processing was performed to calculate the average molecular weight and the polydispersity. (2) Evaluation of thread cutting property at the time of covering the elastic fiber: The elastic fiber cheese is stored in a polyethylene bag at 25 ° C. for one month, and then covered. The covering process is performed by a covering machine ON-741S manufactured by Ozeki Techno Co., Ltd.
85 mm of 20-denier 2-filament elastic fiber
φ, elastic fiber cheese wound on a 50 mm wide paper tube,
Polyamide fiber (manufactured by Asahi Kasei Corporation, Leona 10d /
Attach 5f) cheese and keep at 10 ° C. for 16 hours. Thereafter, the outside air temperature is raised to 15 ° C., and after 5 minutes, covering of the elastic fiber is started. Covering conditions are draft rate 2.
7, twist number 1600T / m, single cover S twist, Z
Twist. The winding ratio of the covered SCY was 0.95 times the covering roll speed. The cheese is set on a covering machine with a total of 10 spindles, operated for 10 minutes after the start of the covering, the thread is cut by reverse winding or loosening, and the number of spindles at which the processing machine stops is counted.
Elastic fibers with more than are determined to be unsuitable. (3) Measurement of cyclic oligomer: Copolymerized PTMG was diluted with twice the amount of chloroform, and gas chromatography column: Silicone SE-30 10 wt% / Chromosolve WHP × 1 m
(Glass) The reaction was performed at a column temperature of 295 ° C. (4) Measurement of composition ratio 1H. 13C-NMR (JEOL-G manufactured by JEOL Ltd.)
X 400). [Example 1] (Production of polyurethane urea elastic fiber) A container equipped with a stirrer and a reflux condenser is charged with 500 g of THF and 56 g of neopentyl glycol. After adding 500 g of anhydrous tungstic acid which was heated at 340 ° C. for 3 hours and made anhydrous, the mixture was stirred and reacted at 60 ° C. for 10 hours in a dry nitrogen gas atmosphere, and then separated into two phases when allowed to stand at room temperature. . The upper layer was separated, and unreacted THF and neopentyl glycol were removed by distillation to obtain 140 g of a transparent and viscous polyalkylene ether diol. As a result of analysis, the number average molecular weight was 2,000, the ratio of the side chain-containing unit was 15%, and the content of the cyclic oligomer having a repeating unit of 9 or less was 4%.
【００２３】該ポリアルキレンエーテルジオール１００
ｇに純水１００g を加え、３０℃で２０分攪拌した。そ
の後室温で１８時間放置し、上層に共重合ＰＴＭＧを、
下層に水層を分離し触媒を除去した。上層液中のポリア
ルキレンエーテルジオールは薄膜減圧加熱下でオリゴマ
ーを除去し、数平均分子量、側鎖含有単位の比率、繰り
返し単位９以下の環状オリゴマー含有量を測定し、表１
の結果を得た。The polyalkylene ether diol 100
100 g of pure water was added to the resulting mixture, and the mixture was stirred at 30 ° C. for 20 minutes. Then, it was left at room temperature for 18 hours, and the copolymerized PTMG was
The aqueous layer was separated as a lower layer, and the catalyst was removed. The polyalkylene ether diol in the upper layer solution was subjected to thin film thin film heating under reduced pressure to remove the oligomer, and the number average molecular weight, the ratio of the side chain content unit, and the cyclic oligomer content of 9 or less repeating units were measured.
Was obtained.
【００２４】該共重合ポリアルキレンエーテルジオール
２、０００ｇと４，４−ジフェニルメタンジイソシアネ
ート（以下ＭＤＩと略記）４００ｇ（１．６モル）とを
乾燥窒素下で８０℃で３時間、攪拌下で反応させて、プ
レポリマーを得た。これを室温に冷却した後、ジメチル
アセトアミド４、４５７ｇを加え、室温で攪拌しながら
溶解し、均一なプレポリマー溶液とした。2,000 g of the copolymerized polyalkylene ether diol and 400 g (1.6 mol) of 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) are reacted under dry nitrogen at 80 ° C. for 3 hours with stirring. Thus, a prepolymer was obtained. After cooling to room temperature, 4,457 g of dimethylacetamide was added and dissolved with stirring at room temperature to obtain a uniform prepolymer solution.
【００２５】一方、エチレンジアミン３４．２ｇ（０．
５７モル）、ジエチルアミン４．３８ｇ（０．０６モ
ル）をジメチルアセトアミド１、２３３ｇに溶解した溶
液を、上記プレポリマー溶液に高速攪拌下で一気に加
え、さらに室温下１時間反応させ、ポリウレタンウレア
を得た。この溶液に、酸化防止剤、黄変防止剤、等の添
加剤を所定量添加混合して乾式紡糸原液とした。紡糸原
液全体の固形分濃度は、約３５％とした。この紡糸原液
を乾式紡糸機に供給し、８００ｍ／分の巻き取り速度
で、２０デニールの２フィラメント弾性繊維を８５ｍｍ
φ、幅５０ｍｍの紙管に４５０ｇ巻き取った。 （カバリング加工）上記弾性繊維チーズをポリエチレン
袋中で２５℃・１ヶ月放置後、カバリング加工を行っ
た。カバリング加工機の停止台数が０％であった。カバ
リング加工時の糸切れ性評価試験を１０回繰り返した
が、１０回ともスタート後１０分以内は糸切れが生じな
かった。本実施例では、メチル基側鎖を１５％有し、低
温伸長時の結晶化が小さく、低温度での伸長回復性が阻
害されなかったと思われる。また環状オリゴマーの含有
量も、原料ジオールで０．８重量％と低く、弾性繊維表
面へのブリードが少なく、粘着性が弱く逆巻きが起こら
なかったと思われる。 [ 実施例２] （ポリウレタンウレア弾性繊維の製造）実施例１と同様
の方法で共重合ポリアルキレンエーテルジオールを重合
し、薄膜減圧加熱下でオリゴマーを除去し、数平均分子
量、側鎖含有単位の比率、繰り返し単位９以下の環状オ
リゴマー含有量を測定し、表１の結果を得た。On the other hand, 34.2 g of ethylenediamine (0.
57 mol) and a solution obtained by dissolving 4.38 g (0.06 mol) of diethylamine in 1,233 g of dimethylacetamide were added to the above prepolymer solution at a stretch under high-speed stirring, and further reacted at room temperature for 1 hour to obtain a polyurethaneurea. Was. A predetermined amount of additives such as an antioxidant and an anti-yellowing agent were added to this solution and mixed to obtain a dry spinning dope. The solid content concentration of the entire spinning dope was about 35%. This spinning solution is supplied to a dry spinning machine, and a 20-denier two-filament elastic fiber is fed to a dry spinning machine at a winding speed of 800 m / min.
450 g was wound around a paper tube having a φ and a width of 50 mm. (Covering) The above elastic fiber cheese was left in a polyethylene bag at 25 ° C. for one month, and then covered. The number of stopped covering machines was 0%. The yarn breakability evaluation test at the time of the covering process was repeated 10 times, but no yarn break occurred within 10 minutes after the start. In this example, it is considered that the resin had 15% of a methyl group side chain, crystallization at low temperature extension was small, and extension recovery at low temperature was not inhibited. Also, the content of the cyclic oligomer was as low as 0.8% by weight of the raw material diol, the bleeding to the elastic fiber surface was small, the tackiness was weak, and it was considered that reverse winding did not occur. [Example 2] (Production of polyurethane urea elastic fiber) Copolymerized polyalkylene ether diol was polymerized in the same manner as in Example 1, and the oligomer was removed under reduced pressure and heated under reduced pressure. The ratio and the content of the cyclic oligomer having a repeating unit of 9 or less were measured, and the results shown in Table 1 were obtained.
【００２６】実施例１と同様に、重合・紡糸を行い弾性
繊維を得、これを１ヶ月放置後カバリング加工を行っ
た。カバリング加工機の停止台数が０％であった。カバ
リング加工時の糸切れ性評価試験を１０回繰り返した
が、１０回ともスタート後１０分以内は糸切れが生じな
かった。 [ 比較例１] （ポリウレタンウレア弾性繊維の製造）実施例１と同様
の方法で共重合ポリアルキレンエーテルジオールを重合
し、薄膜減圧加熱下でオリゴマーを除去し、数平均分子
量、側鎖含有単位の比率、繰り返し単位９以下の環状オ
リゴマー含有量を測定し、表１の結果を得た。In the same manner as in Example 1, polymerization and spinning were performed to obtain an elastic fiber, which was left for one month and then covered. The number of stopped covering machines was 0%. The yarn breakability evaluation test at the time of the covering process was repeated 10 times, but no yarn break occurred within 10 minutes after the start. [Comparative Example 1] (Production of polyurethane urea elastic fiber) Copolymerized polyalkylene ether diol was polymerized in the same manner as in Example 1, and the oligomer was removed under reduced pressure heating under reduced pressure. The ratio and the content of the cyclic oligomer having a repeating unit of 9 or less were measured, and the results shown in Table 1 were obtained.
【００２７】実施例１と同様に、重合・紡糸を行い弾性
繊維を得、これを１ヶ月放置後カバリング加工を行っ
た。カバリング加工機の停止台数が３０％であった。カ
バリング加工時の糸切れ性評価試験を１０回繰り返し、
１０回のうち１０分以内での糸切れは３回起こった。本
比較例では、メチル基側鎖を１６％有し、低温伸長時の
結晶化が小さく、低温度での伸長回復性が阻害されなか
ったと思われる。その一方環状オリゴマーの含有量は原
料ジオールで３．８重量％と高く、弾性繊維表面の粘着
性が大きくなり、逆巻きのため糸切れ率が高くなったと
思われる。 [ 実施例３] （ポリウレタンウレア弾性繊維の製造）攪拌装置と環流
冷却器とを付けた容器に、ＴＨＦ５００ｇと水１．６ｇ
を仕込む。３４０℃で３時間加熱して無水状態にした隣
タングステン酸を５０ｇ加え、乾燥窒素ガス雰囲気下、
６０℃に保持して、攪拌下、３、３−ジエチルオキセタ
ン９０ｇを０．７５ｇ／分の速度で滴下した後、６０℃
に保ちたまま、６時間攪拌下で反応させる。室温で静置
すると二相に分離し、上澄み液か未反応のＴＨＦ、３，
３−ジメチルオキセタンを除去し、透明で粘性のあるポ
アルキレンエーテルジオール１５３ｇを得た。In the same manner as in Example 1, polymerization and spinning were performed to obtain an elastic fiber, which was left for one month and covered. The number of stopped covering machines was 30%. Repeat the yarn breakability evaluation test at the time of covering process 10 times,
Thread breaks within 10 minutes out of 10 occurred 3 times. In this comparative example, it is thought that it has 16% of methyl group side chains, crystallization at low temperature extension is small, and extension recovery at low temperature is not inhibited. On the other hand, the content of the cyclic oligomer was as high as 3.8% by weight in the raw material diol, and the adhesiveness of the elastic fiber surface was increased. [Example 3] (Production of polyurethane urea elastic fiber) In a vessel equipped with a stirrer and a reflux condenser, 500 g of THF and 1.6 g of water were placed.
Prepare. Add 50 g of anhydrous tungstic acid which was heated at 340 ° C. for 3 hours to make it anhydrous, and dried under a nitrogen gas atmosphere.
After maintaining at 60 ° C and stirring, 90 g of 3,3-diethyloxetane was added dropwise at a rate of 0.75 g / min.
The reaction is carried out under stirring for 6 hours while maintaining the temperature. Upon standing at room temperature, it separates into two phases and the supernatant or unreacted THF, 3,
3-dimethyloxetane was removed to obtain 153 g of a transparent and viscous polyalkylene ether diol.
【００２８】該ポリアルキレンエーテルジオール１００
ｇに純水１００g を加え、３０℃で２０分攪拌した。そ
の後室温で１８時間放置し、上層に共重合ＰＴＭＧを、
下層に水層を分離し触媒を除去した。上層液中のポリア
ルキレンエーテルジオールは薄膜減圧加熱下でオリゴマ
ーを除去し、数平均分子量、側鎖含有単位の比率、繰り
返し単位９以下の環状オリゴマー含有量を測定し、表１
の結果を得た。The polyalkylene ether diol 100
100 g of pure water was added to the resulting mixture, and the mixture was stirred at 30 ° C. for 20 minutes. Then, it was left at room temperature for 18 hours, and the copolymerized PTMG was
The aqueous layer was separated as a lower layer, and the catalyst was removed. The polyalkylene ether diol in the upper layer solution was subjected to thin film thin film heating under reduced pressure to remove the oligomer, and the number average molecular weight, the ratio of the side chain content unit, and the cyclic oligomer content of 9 or less repeating units were measured.
Was obtained.
【００２９】該共重合ポリアルキレンエーテルジオール
を実施例１同様にＭＤＩと反応させプレポリマーとし、
ジメチルアセトアミドにエチレンジアミン、ジエチルア
ミンを溶解した溶液を、上記プレポリマー溶液に高速攪
拌下で一気に加え、さらに室温下１時間反応させポリウ
レタンウレアを得た。この溶液に、酸化防止剤、黄変防
止剤、等の添加剤を所定量添加混合して乾式紡糸原液と
した。紡糸原液全体の固形分濃度は、約３５％とした。
この紡糸原液を乾式紡糸機に供給し、８００ｍ／分の巻
き取り速度で、２０デニールの２フィラメント弾性繊維
を８５ｍｍφ、幅５０ｍｍの紙管に４５０ｇ巻き取っ
た。The copolymerized polyalkylene ether diol was reacted with MDI in the same manner as in Example 1 to obtain a prepolymer.
A solution obtained by dissolving ethylenediamine and diethylamine in dimethylacetamide was added to the above prepolymer solution at a stretch under high-speed stirring, and further reacted at room temperature for 1 hour to obtain polyurethaneurea. A predetermined amount of additives such as an antioxidant and an anti-yellowing agent were added to this solution and mixed to obtain a dry spinning dope. The solid content concentration of the entire spinning dope was about 35%.
This spinning stock solution was supplied to a dry spinning machine, and at a winding speed of 800 m / min, 450 g of a 20-denier 2-filament elastic fiber was wound around a paper tube having a diameter of 85 mm and a width of 50 mm.
【００３０】カバリング加工時の糸切れ性評価試験を１
０回繰り返し、１０回のうち１０分以内での糸切れは０
回と良好であった。An evaluation test for yarn breakability during the covering process was performed as follows.
0 repetitions 0 times of thread break within 10 minutes out of 10 times
Good times.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【発明の効果】本発明によれば、低温度の下での急激な
伸長回復性、特に伸長回復速度の低下が改善されてお
り、また繊維に粘着によっておこるチーズの逆巻きに発
生が少ないポリウレタンウレア系弾性繊維を得ることが
できる。本発明のポリウレタンウレア弾性繊維を用いる
ことにより、カバリング加工が寒冷期に低温下で行われ
ても、チーズ巻体が解除に逆巻きを起すことがなく、か
つまた被覆後に被覆弾性糸を弛み糸切れを起すことなく
安定してチーズ上に巻取ることができる。According to the present invention, polyurethane urea which has improved rapid recovery at low temperatures, especially a reduction in the recovery speed, and has little occurrence of reverse winding of cheese caused by sticking to fibers. A system elastic fiber can be obtained. By using the polyurethane urea elastic fiber of the present invention, even if the covering process is performed at a low temperature in the cold season, the cheese roll does not cause reverse winding upon release, and the coated elastic yarn is loosened after coating and the yarn breaks. Can be stably wound on cheese without causing cracks.
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Claims (1)
有量が１．５％以下でありメチル基側鎖を有する共重合
ポリアルキレンエーテルジオールをジオール成分として
なるポリウレタンウレア系弾性繊維。1. A polyurethane urea-based elastic fiber comprising a copolymerized polyalkylene ether diol having a cyclic oligomer content of not more than 9 repeating units of not more than 1.5% and having a methyl group side chain as a diol component.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18193099A JP4270655B2 (en) | 1999-06-28 | 1999-06-28 | Copolymer elastic fiber with good low-temperature covering properties |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18193099A JP4270655B2 (en) | 1999-06-28 | 1999-06-28 | Copolymer elastic fiber with good low-temperature covering properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001011732A true JP2001011732A (en) | 2001-01-16 |
| JP4270655B2 JP4270655B2 (en) | 2009-06-03 |
Family
ID=16109392
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18193099A Expired - Lifetime JP4270655B2 (en) | 1999-06-28 | 1999-06-28 | Copolymer elastic fiber with good low-temperature covering properties |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018220983A1 (en) * | 2017-05-30 | 2018-12-06 | 保土谷化学工業株式会社 | Method for producing biopolyether polyol, biopolyether polyol, and biopolyurethane resin |
-
1999
- 1999-06-28 JP JP18193099A patent/JP4270655B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018220983A1 (en) * | 2017-05-30 | 2018-12-06 | 保土谷化学工業株式会社 | Method for producing biopolyether polyol, biopolyether polyol, and biopolyurethane resin |
| JPWO2018220983A1 (en) * | 2017-05-30 | 2020-04-16 | 保土谷化学工業株式会社 | Biopolyether polyol production method, biopolyether polyol and biopolyurethane resin |
| US11279792B2 (en) | 2017-05-30 | 2022-03-22 | Hodogaya Chemical Co., Ltd. | Method for producing a biopolyether polyol, biopolyether polyol, and biopolyurethane resin |
| JP2022079647A (en) * | 2017-05-30 | 2022-05-26 | 保土谷化学工業株式会社 | Method for producing bio-polyether polyol, bio-polyether polyol and bio-polyurethane resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4270655B2 (en) | 2009-06-03 |
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